CN117282975A - Superfine silver powder for HJT low-temperature silver paste and preparation method thereof - Google Patents
Superfine silver powder for HJT low-temperature silver paste and preparation method thereof Download PDFInfo
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- CN117282975A CN117282975A CN202311236586.7A CN202311236586A CN117282975A CN 117282975 A CN117282975 A CN 117282975A CN 202311236586 A CN202311236586 A CN 202311236586A CN 117282975 A CN117282975 A CN 117282975A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 239000004332 silver Substances 0.000 title claims abstract description 63
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 74
- 239000002245 particle Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000002270 dispersing agent Substances 0.000 claims description 42
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 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 28
- 238000000498 ball milling Methods 0.000 claims description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 26
- 239000004925 Acrylic resin Substances 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 229920000178 Acrylic resin Polymers 0.000 claims description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 15
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 14
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 14
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000005642 Oleic acid Substances 0.000 claims description 14
- 229930003268 Vitamin C Natural products 0.000 claims description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 14
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 14
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 14
- 235000019154 vitamin C Nutrition 0.000 claims description 14
- 239000011718 vitamin C Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Chemical group CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910001923 silver oxide Inorganic materials 0.000 claims description 7
- 150000002460 imidazoles Chemical group 0.000 claims description 6
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 claims description 5
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 230000002776 aggregation Effects 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000005054 agglomeration Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 6
- 239000010946 fine silver Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 244000208060 Lawsonia inermis Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Classifications
-
- 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
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses superfine silver powder for HJT low-temperature silver paste and a preparation method thereof, wherein the silver powder is of a third type, has a simple preparation method, excellent properties, excellent bulk resistance conductivity and excellent contact resistance after curing, and can meet the technical requirements of silver powder required by HJT silver paste on the market.
Description
Technical Field
The invention belongs to the technical field of solar silver paste, and particularly relates to superfine silver powder for HJT low-temperature silver paste and a preparation method thereof.
Background
With the development of solar crystalline silicon heterojunction solar cell (Heterojunction Technology, HJT) technology, the application and technical development of low-temperature HJT silver paste are increasingly paid attention to. HJT silver paste is required to be capable of being printed at room temperature, the curing temperature is lower than 200 ℃, the cured silver wire circuit has very good bulk resistance, and the cured silver wire circuit can form relatively good contact resistance with a substrate material at the lower layer. Most of HJT silver paste in the current market is still required to be imported, and the biggest reason is that no mature mass production technology exists in China in the silver powder serving as a key material, and the domestic silver powder used for HJT technology is still blank at present. The currently known silver powder for HJT technology is divided into three types, namely a flake silver powder with high tap density, a semi-flake silver powder with high tap density and an ultrafine silver powder with tap density of more than 5, wherein the particle size distribution of the silver powder is between 0.3 and 0.4 microns. The third type of superfine silver powder with tap density larger than 5 has the largest proportion in low-temperature HJT silver paste, and has great influence on the performance of the low-temperature HJT silver paste, especially on the bulk resistance, and the technical difficulty of the silver powder mass production is the highest recognized in industry.
The traditional synthesis and separation of the superfine silver powder with the high tap density and the distribution particle size of 0.3-0.4 microns have the following technical difficulties:
firstly, the distribution particle size is concentrated, and a relatively large amount of dispersing agent is adopted in the synthesis process, so that the dispersing agent can effectively disperse during silver powder synthesis, so that enough space is kept between silver powder particles, a hard aggregation state cannot be formed in the synthesis process, and the current requirement of silver powder cannot be met;
secondly, if the surface energy of the synthesized silver powder is too high, after the silver powder is separated from the solution, the silver powder with larger surface energy can be finally changed into polycrystalline large-particle silver powder, so that the particle size distribution of the silver powder can not meet the requirement;
finally, the dispersing agent can be easily cleaned and removed after the silver powder is synthesized, and the silver powder and the solution are easily separated. The problem with such ultra-fine silver powder made from the dispersants like PVP, hydroxyethyl cellulose, gelatin, and arabinon mentioned in other patents is that during the synthesis stage, the silver powder performance can be kept in a good dispersion state in the mixed state of the solution and the silver powder, but once the subsequent separation of the silver powder and the solution is performed, the problems of agglomeration of the silver powder particles, enlargement of the silver powder particles, suspension of the silver powder particles in the solution, and the like occur.
Disclosure of Invention
In order to solve the technical problems, the invention provides the superfine silver powder for HJT low-temperature silver paste and the preparation method thereof, wherein the silver powder is the third type of superfine silver powder, has simple preparation method, excellent properties, excellent bulk resistance conductivity and excellent contact resistance after solidification, and can meet the technical requirements of the silver powder required by HJT silver paste on the market.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the superfine silver powder for HJT low-temperature silver paste comprises the following steps:
1) Uniformly mixing silver nitrate and deionized water according to the mass ratio of 1 (5-20), stirring and dissolving in a reaction kettle A, controlling the temperature to be (30+/-1) DEG C, and maintaining the time for 5-10min; then adding alkali solution according to the mass ratio of silver nitrate to alkali solution of 1 (2-3), wherein the mass ratio of alkali to water in the alkali solution is 1: (3-5) generating silver oxide suspension, and then adding a mixed dispersing agent into the suspension, wherein the total addition amount of the mixed dispersing agent is 5-30% of the mass of the silver nitrate;
2) Adding deionized water, vitamin C and a mixed dispersing agent into a reaction kettle B, wherein the mass ratio of the added vitamin C to the silver nitrate is (1-1.5): 1, the total added amount of the mixed dispersing agent is 5-30% of the mass of the silver nitrate, the temperature is controlled at (30+/-1) DEG C, and the time is maintained for 5-10min;
the mixed dispersing agent in the step 1) and the step 2) is the mixture of a dispersing agent A and a dispersing agent B, wherein the mass ratio of the dispersing agent A to the dispersing agent B is (10-20) 1, the dispersing agent A is selected from phosphorus element or sulfonic polyether modified acrylic resin, and the dispersing agent B is selected from imidazole or imidazole derivatives;
3) Slowly adding the solution in the reaction kettle B into the reaction kettle A at a constant speed for 5-10min, continuously stirring for 10-15min after all the solution is added, adding an alcohol solution which is equivalent to 1-2 permillage of the mass of silver nitrate and is dissolved with oleic acid for silver powder coating treatment, and rapidly separating the silver powder from the solution after 5-10min, wherein the mass concentration of the alcohol solution which is dissolved with oleic acid is 15-25%;
4) Adding silver powder obtained by separation in the previous step into a ball milling tank, and adding zirconium balls with the diameter of 1mm into the ball milling tank, wherein the mass ratio of silver nitrate to the zirconium balls is 1:4; adding alcohol, wherein the mass ratio of the silver nitrate to the alcohol is 1 (0.5-0.8), and ball milling for 2-5 hours according to 80-100 revolutions per minute; and then separating silver powder, alcohol and zirconium balls by using a 100-mesh screen, continuously separating the silver powder from the alcohol by using a suction filtration mode, and freeze-drying to obtain the superfine silver powder with tap density of more than 5, wherein the particle size distribution of the silver powder is 0.2, 0.3-0.4 and 0.6 of D50, and the particle sizes are very concentrated.
In the invention, the following components are added:
the strong base described in step 1) is preferably sodium hydroxide.
The dispersing agent A in the step 1) and the step 2) is phosphorus element or sulfonic polyether modified acrylic resin, preferably phosphorus element modified acrylic resin or sulfonic polyether modified acrylic resin, and the dispersing agent has the functions of enabling the particle size of the generated silver powder to be smaller, and has very good dispersing performance in a solution, no hard agglomeration, separated particles and uniform and concentrated particle size of the silver powder within the required particle size distribution range of 0.3-0.4 microns. The key is that the dispersing agent is easy to dissolve in water and alcohol in the cleaning process of silver powder, and can not adhere to the surface of the silver powder, so that the silver powder is easy to realize and the solution is easy to separate. The dispersing agent B is imidazole or imidazole derivatives, preferably imidazole or methylimidazole, and has the function of enabling the generated silver powder to present a polyhedral complete crystal phase structure, wherein the polyhedral crystal phase can enable the surface energy of the silver powder to be reduced, and particles are kept in an independent and separated state in a drying treatment process and ball milling process required after the synthesis of the superfine silver powder, so that hard agglomeration caused by overlarge surface energy in the drying moisture and ball milling process can be avoided.
The addition amount of the mixed dispersing agent in the step 1 and the step 2) is 5-30% of the weight of the silver nitrate; if the ratio is smaller than the above ratio, the effect of the mixed dispersing agent is not obvious, and problems such as particle enlargement and agglomeration of silver powder can occur; if the amount added exceeds this ratio, the particle size of the silver powder will decrease and agglomeration will easily occur, thereby failing to reach the particle size distribution range and tap density range of the silver powder required in the present patent.
The mass ratio of the phosphorus element or sulfonic polyether modified acrylic resin to the imidazole or imidazole derivative in the step 1 and the step 2) is (10-20): 1; if the proportion of the phosphorus element or the sulfonic polyether modified acrylic resin is too high, large-particle polycrystalline agglomerated silver powder is easy to form in the drying and ball milling processes of the silver powder; if the ratio is too low, the silver powder is easy to generate an agglomeration state in the synthesis process of the reaction liquid, and the required performance of the silver powder of the patent cannot be achieved.
The rapid separation in the step 3) is realized by using a suction filtration mode to rapidly separate silver powder from deionized water, and alcohol with the mass concentration of 10-30% is used for cleaning in the last two times, and the water in the silver powder subjected to ball milling can be reduced to a negligible state due to the dehydration and rapid volatilization of the alcohol.
The invention also relates to the superfine silver powder for HJT low-temperature silver paste, which is obtained by adopting the preparation method of the superfine silver powder for HJT low-temperature silver paste, and has the tap density of more than 5, wherein the particle size distribution of the superfine silver powder is that D10 is 0.20-0.23, D50 is 0.30-0.40, D90 is 0.60-0.63, and the particle sizes are very concentrated.
Compared with the prior art, the invention has the following advantages:
1. according to the preparation method of the superfine silver powder for HJT low-temperature silver paste, the pH and the temperature do not need to be specially adjusted in the production process, the reaction can be completed at normal temperature, and the reaction energy consumption is reduced; in addition, compared with the traditional process, the preparation method provided by the invention has the advantages that the process is relatively simple, the reaction time is short, the production efficiency is greatly improved, and the production cost is saved.
2. According to the preparation method of the superfine silver powder for HJT low-temperature silver paste, in the synthesis and distribution optimization of silver powder particles, a double-dispersing agent mode is adopted, wherein the dispersing agent of phosphorus element or sulfonic polyether modified acrylic resin optimizes the whole concentration degree and particle size distribution range of the silver powder particles, imidazole or imidazole derivatives optimize the surface crystal form condition of the particle state of the silver powder, so that the surface energy of the superfine silver powder after synthesis is greatly reduced, the synthesized silver powder is easy to separate from a liquid phase, agglomeration and the like caused by over-high activity in the ball milling and drying processes at the later stage are avoided, and the silver powder dispersing agent produced by the method is easy to be subjected to removal treatment by water and alcohol, and cannot adhere to the surface of the silver powder, so that the silver powder is suspended in water and is not well separated in the washing process; the whole production process is extremely simple and easy to operate, and large-scale production is realized.
Drawings
FIG. 1 is an SEM image of an ultrafine silver powder for HJT low-temperature silver paste prepared in example 1 of the present invention;
fig. 2 is an SEM image of the ultra-fine silver powder for HJT low-temperature silver paste prepared in comparative example 1 of the present invention;
FIG. 3 is an SEM image of the ultra-fine silver powder for HJT low-temperature silver paste prepared in comparative example 2 of the present invention;
FIG. 4 is a HJT low-temperature silver paste print pattern of the ultrafine silver powder prepared in example 1 of the present invention ((a) is a top view of a printed wiring of HJT low-temperature silver paste made of the silver powder of FIG. 1; b) is a side view of a printed wiring of HJT low-temperature silver paste made of the silver powder of FIG. 1);
FIG. 5 is a HJT low-temperature silver paste print pattern of the ultrafine silver powder produced in comparative example 1 of the present invention (5 (a) is a top view of a printed wiring of HJT low-temperature silver paste produced using the silver powder of FIG. 2; b) is a side view of a printed wiring of HJT low-temperature silver paste produced using the silver powder of FIG. 2);
fig. 6 is a HJT low-temperature silver paste print pattern of the ultra-fine silver powder prepared in comparative example 2 of the present invention ((a) is a top view of a printed wiring of HJT low-temperature silver paste made of the silver powder of fig. 3; b) is a side view of a printed wiring of HJT low-temperature silver paste made of the silver powder of fig. 3).
Detailed Description
The present invention is described in further detail by the following examples, which should not be construed as limiting the invention. Unless otherwise indicated, all starting materials and equipment used in the examples herein were purchased commercially, and all methods used in the examples, unless otherwise indicated, were conventional in the art.
Example 1:
the preparation method of the superfine silver powder for HJT low-temperature silver paste comprises the following steps:
firstly, mixing and stirring 16 kg of silver nitrate and 100 liters of deionized water in a reaction kettle A to dissolve, and controlling the water temperature to be 35 ℃;
in the second step, 7 kg of strong base (sodium hydroxide) was dissolved in 30 liters of deionized water, then a strong base solution was added to the a reactor to produce a silver oxide suspension, and then 1 kg of phosphorus element modified acrylic resin (Hunan Unikko Co.) and 200g of methylimidazole (Ala Ding Gongsi) were added to the suspension, and the solution was stirred and stirred. Then 11 kg of vitamin C is dissolved in 50L of deionized water in a B kettle, 1 kg of phosphorus element modified acrylic resin (Hunan Younike) and 200g of methylimidazole (Ala Ding Gongsi) are added into the vitamin C solution, then the solution in the reaction B kettle is slowly added into the reaction kettle A at a constant speed, the adding time is controlled to be 5min, stirring is continuously carried out, after all the solution is added, stirring is continued for 5min, then an alcohol solution which is equivalent to 1 per mill of the silver nitrate in mass and is dissolved with oleic acid is added for silver powder coating treatment, wherein the mass concentration of the alcohol solution which is dissolved with oleic acid is 15%, and the silver powder and the solution are rapidly separated after 10 min.
Adding silver powder obtained by separation in the previous step into a ball milling tank, and adding zirconium balls with the diameter of 1mm into the ball milling tank, wherein the mass ratio of silver nitrate to the zirconium balls is 1:4; adding alcohol, wherein the mass ratio of the silver nitrate to the alcohol is 1:0.5, and performing ball milling treatment for 2 hours according to 80 revolutions per minute; then separating silver powder, alcohol and zirconium balls by using a 100-mesh screen, continuously realizing the separation of the silver powder and the alcohol by using a suction filtration mode, and finally obtaining the superfine silver powder with tap density of 5.7 by freeze drying, wherein the particle size distribution of the silver powder is D10 of 0.21, D50 of 0.35 and D90 of 0.61, the particle sizes are very concentrated, SEM pictures are shown in figure 1, the silver powder particles are well dispersed, and the particle sizes meet the requirements:
FIG. 1 is an SEM image of an ultrafine silver powder for HJT low-temperature silver paste prepared in example 1;
FIG. 4 is a HJT low-temperature silver paste print pattern of the ultrafine silver powder prepared in example 1 ((a) is a top view of a printed wiring of HJT low-temperature silver paste made of the silver powder of FIG. 1, and (b) is a side view of a printed wiring of HJT low-temperature silver paste made of the silver powder of FIG. 1).
Example 2:
the preparation method of the superfine silver powder for HJT low-temperature silver paste comprises the following steps:
firstly, mixing and stirring 16 kg of silver nitrate and 100 liters of deionized water in a reaction kettle A to dissolve, and controlling the water temperature to be 35 ℃;
in the second step, 7 kg of strong base (sodium hydroxide) was dissolved in 30 liters of deionized water, then a strong base solution was added to the a reaction vessel to form a silver oxide suspension, and then 1 kg of sulfonic acid group polyether-modified acrylic resin (Hunan Unikko Co.) and 200g of methylimidazole (Ala Ding Gongsi) were added to the suspension, and the solution was stirred and stirred. Then 11 kg of vitamin C is dissolved in 50L of deionized water, then 1 kg of sulfonic polyether modified acrylic resin (Hunan Youkouke) and 200g of methylimidazole (Ala Ding Gongsi) are added into the vitamin C solution, then the solution in the reaction B kettle is slowly added into the reaction kettle A at a constant speed, the adding time is controlled to be 5min, stirring is continuously carried out, after all the solution is added, stirring is continued for 5min, then an alcohol solution which is equivalent to 2 per mill of the mass of silver nitrate and is dissolved with oleic acid is added for silver powder coating treatment, wherein the mass concentration of the alcohol solution which is dissolved with oleic acid is 15%, and the silver powder and the solution are rapidly separated after 10 min.
Adding silver powder obtained by separation in the previous step into a ball milling tank, and adding zirconium balls with the diameter of 1mm into the ball milling tank, wherein the mass ratio of silver nitrate to the zirconium balls is 1:4; adding alcohol, wherein the mass ratio of the silver nitrate to the alcohol is 1:0.6, and performing ball milling treatment for 2 hours according to 80 revolutions per minute; and then separating silver powder, alcohol and zirconium balls by using a 100-mesh screen, continuously separating the silver powder from the alcohol by using a suction filtration mode, and freeze-drying to obtain the superfine silver powder with tap density of 5.6, wherein the particle size distribution of the silver powder is D10 of 0.22, D50 of 0.38 and D90 of 0.62, and the particle sizes are very concentrated.
Example 3:
the preparation method of the superfine silver powder for HJT low-temperature silver paste comprises the following steps:
firstly, mixing and stirring 16 kg of silver nitrate and 100 liters of deionized water in a reaction kettle A to dissolve, and controlling the water temperature to be 35 ℃;
in the second step, 7 kg of strong base (potassium hydroxide) was dissolved in 30 liters of deionized water, then a strong base solution was added to the a reactor to produce a silver oxide suspension, and then 1 kg of phosphorus element modified acrylic resin (Hunan Unikko Co.) and 200g of imidazole (Ala Ding Gongsi) were added to the suspension, and the solution was stirred and stirred. Then 11 kg of vitamin C is dissolved in 50L of deionized water in a B kettle, 1 kg of phosphorus element modified acrylic resin (Hunan Youkouke company) and 200g of imidazole (Abra Ding Gongsi) are added into the vitamin C solution, then the solution in the reaction B kettle is slowly added into the reaction kettle A at a constant speed, the adding time is controlled to be 5min, stirring is continuously carried out, after all the solution is added, stirring is continued for 5min, then an alcohol solution which is equivalent to 1 per mill of the silver nitrate in mass and is dissolved with oleic acid is added for silver powder coating treatment, wherein the mass concentration of the alcohol solution which is dissolved with oleic acid is 15%, and the silver powder and the solution are rapidly separated after 10 min.
Adding silver powder obtained by separation in the previous step into a ball milling tank, and adding zirconium balls with the diameter of 1mm into the ball milling tank, wherein the mass ratio of silver nitrate to the zirconium balls is 1:4; adding alcohol, wherein the mass ratio of the silver nitrate to the alcohol is 1:0.8, and performing ball milling treatment for 2 hours according to 80 revolutions per minute; and then separating silver powder, alcohol and zirconium balls by using a 100-mesh screen, continuously separating the silver powder from the alcohol by using a suction filtration mode, and freeze-drying to obtain the superfine silver powder with tap density of 5.3, wherein the particle size distribution of the silver powder is D10 of 0.23, D50 of 0.37 and D90 of 0.63, and the particle sizes are very concentrated.
Comparative example 1:
comparative example 1 differs from example 1 in that the amount of methylimidazole added in the dispersant was reduced;
the method for preparing the superfine silver powder for HJT low-temperature silver paste comprises the following steps of:
firstly, mixing and stirring 16 kg of silver nitrate and 100 liters of deionized water in a reaction kettle A to dissolve, and controlling the water temperature to be 35 ℃;
in the second step, 7 kg of strong base (sodium hydroxide) was dissolved in 30 liters of deionized water, then a strong base solution was added to the a reactor to form a silver oxide suspension, and then 1 kg of phosphorus element or sulfonic polyether modified acrylic resin (henna) and 10g of methylimidazole (ala Ding Gongsi) were added to the suspension, followed by stirring for dissolution. Then 11 kg of vitamin C is dissolved in 50L of deionized water in a B kettle, 1 kg of phosphorus element modified acrylic resin (Hunan Youkouke) and 10g of methylimidazole (Ala Ding Gongsi) are added into the vitamin C solution, then the solution in the reaction B kettle is slowly added into the reaction kettle A at a constant speed, the adding time is controlled to be 5min, stirring is continuously carried out, after all the solution is added, stirring is continuously carried out for 5min, then an alcohol solution which is equivalent to 1 per mill of the mass of silver nitrate and is dissolved with oleic acid is added for silver powder coating treatment, wherein the mass concentration of the alcohol solution which is dissolved with oleic acid is 15%, and the silver powder and the solution are rapidly separated after 10 min.
Adding silver powder obtained by separation in the previous step into a ball milling tank, and adding zirconium balls with the diameter of 1mm into the ball milling tank, wherein the mass ratio of silver nitrate to the zirconium balls is 1:4; adding alcohol, wherein the mass ratio of the silver nitrate to the alcohol is 1:0.5, and performing ball milling treatment for 2 hours according to 80 revolutions per minute; then separating silver powder, alcohol and zirconium balls by using a 100-mesh screen, continuously separating the silver powder from the alcohol by using a suction filtration mode, and freeze-drying to obtain superfine silver powder B with tap density of 5.1, wherein the particle size distribution of the silver powder is D10 of 0.26, D50 of 0.40 and D90 of 1.6, the silver powder is uniformly dispersed, no obvious agglomeration phenomenon exists, but large particles appear, and SEM pictures are shown in figure 2;
fig. 2 is an SEM image of the ultra-fine silver powder for HJT low-temperature silver paste prepared in comparative example 1;
fig. 5 is a HJT low-temperature silver paste print pattern of the ultrafine silver powder prepared in comparative example 1 (5 (a) is a top view of a printed wiring of HJT low-temperature silver paste made of the silver powder of fig. 2, and (b) is a side view of a printed wiring of HJT low-temperature silver paste made of the silver powder of fig. 2).
Comparative example 2:
comparative example 2 differs from example 1 in that the amount of phosphorus-modified acrylic resin added to the dispersant was reduced;
the method for preparing the superfine silver powder for HJT low-temperature silver paste comprises the following steps of:
firstly, mixing and stirring 16 kg of silver nitrate and 100 liters of deionized water in a reaction kettle A to dissolve, and controlling the water temperature to be 35 ℃;
in the second step, 7 kg of strong base (sodium hydroxide) was dissolved in 30 liters of deionized water, then a strong base solution was added to the a reactor to form a silver oxide suspension, and then 200g of phosphorus element modified acrylic resin (Hunan Unikko Co.) and 200g of methylimidazole (Ala Ding Gongsi) were added to the suspension, and the solution was stirred and stirred. Then 11 kg of vitamin C is dissolved in 50L of deionized water in a B kettle, 200g of phosphorus element modified acrylic resin (Hunan Youkouke company) and 200g of methylimidazole (Ala Ding Gongsi) are added into the vitamin C solution, then the solution in the reaction B kettle is slowly added into the reaction kettle A at a constant speed, the adding time is controlled to be 5min, stirring is continuously carried out, after all the solution is added, stirring is continuously carried out for 5min, then an alcohol solution which is equivalent to 1 per mill of the mass of silver nitrate and is dissolved with oleic acid is added for silver powder coating treatment, wherein the mass concentration of the alcohol solution which is dissolved with oleic acid is 15%, and rapid separation of silver powder and the solution is carried out after 10 min.
Adding silver powder obtained by separation in the previous step into a ball milling tank, and adding zirconium balls with the diameter of 1mm into the ball milling tank, wherein the mass ratio of silver nitrate to the zirconium balls is 1:4; adding alcohol, wherein the mass ratio of the silver nitrate to the alcohol is 1:0.5, and performing ball milling treatment for 2 hours according to 80 revolutions per minute; then separating silver powder, alcohol and zirconium balls by using a 100-mesh screen, continuously separating the silver powder from the alcohol by using a suction filtration mode, and freeze-drying to obtain superfine silver powder C with tap density of 4.3, wherein the particle size distribution of the silver powder is D10 of 0.57, D50 of 0.92 and D90 of 2.9, the silver powder particles are agglomerated, part of particle sizes meet the requirements, but the integral silver powder is obvious in agglomeration, and SEM (scanning electron microscope) pictures are shown in figure 3;
fig. 3 is an SEM image of the ultra-fine silver powder for HJT low-temperature silver paste prepared in comparative example 2;
FIG. 6 is a HJT low-temperature silver paste print pattern of the ultrafine silver powder prepared in comparative example 2 ((a) is a top view of a printed wiring of HJT low-temperature silver paste made using the silver powder of FIG. 3, and (b) is a side view of a printed wiring of HJT low-temperature silver paste made using the silver powder of FIG. 3).
Experimental example:
the silver powders obtained in examples and comparative examples were respectively made into pastes, and the bulk resistance conductive properties and the contact resistance properties after curing were tested:
| project | Bulk resistance | Contact resistance |
| Example 1 | 5.3×10 -6 Ω.cm | 1.50mΩ.cm 2 |
| Example 2 | 5.2×10 -6 Ω.cm | 1.49mΩ.cm 2 |
| Example 3 | 5.3×10 -6 Ω.cm | 1.51mΩ.cm 2 |
| Comparative example 1 | 9.3×10 -6 Ω.cm | 1.53mΩ.cm 2 |
| Comparative example 2 | 2.2×10 -5 Ω.cm | 2.72mΩ.cm 2 |
From the table above, it can be seen that:
1. the superfine silver powder for HJT low-temperature silver paste, which is described in the example, has excellent bulk resistance conductivity (5.2-5.3). Times.10 after curing -6 Omega cm and excellent contact resistance properties (1.49-1.51) momega cm 2 Can meet the technical requirements of silver powder required by HJT silver paste in the market;
2. after the large particles appear in comparative example 1, the prepared slurry has increased resistance and little influence on contact;
3. after the silver powder in comparative example 2 had agglomerated, the resistance of the resulting paste continued to rise and the contact resistance became much higher.
Results and discussion:
1. according to the preparation method of the superfine silver powder for HJT low-temperature silver paste, in the synthesis and distribution optimization of silver powder particles, a double-dispersing agent mode is adopted, wherein the dispersing agent of phosphorus element or sulfonic polyether modified acrylic resin optimizes the whole concentration degree and particle size distribution range of the silver powder particles, imidazole or imidazole derivatives optimize the surface crystal form condition of the particle state of the silver powder, so that the surface energy of the superfine silver powder after synthesis is greatly reduced, the synthesized silver powder is easy to separate from a liquid phase, agglomeration and the like caused by over-high activity in the ball milling and drying processes at the later stage are avoided, and the silver powder dispersing agent produced by the method is easy to be subjected to removal treatment by water and alcohol, and is not adhered to the surface of the silver powder, so that the silver powder is suspended in water and is not well separated in the washing process; the whole production process is extremely simple and easy to operate, and large-scale production is realized.
2. Comparison of example 1 with comparative example 1, comparative example 2 shows that: if the proportion of the phosphorus element or the sulfonic polyether modified acrylic resin is too high, large-particle polycrystalline agglomerated silver powder is easy to form in the drying and ball milling processes of the silver powder; if this ratio is too low, the silver powder is also liable to be in an agglomerated state during the synthesis of the reaction solution, and the desired properties of the silver powder of the present application cannot be achieved.
As can be seen from the HJT low-temperature silver paste print pattern prepared from the silver powder of example 1, the paste print pattern is well shaped and the printing is continuous without broken lines.
As can be seen from the HJT low-temperature silver paste printing pattern prepared from the silver powder prepared in comparative example 1, if the ultrafine silver powder has more large particles, the prepared paste is printed with the problems of partial printing broken lines, discontinuous printing height difference and the like, and the bulk resistance is increased while the contact resistance is not greatly influenced, so that the overall performance of HJT low-temperature silver paste is influenced.
As can be seen from the HJT low-temperature silver paste printing pattern prepared from the silver powder prepared in the comparative example 2, if the superfine silver powder has obvious agglomeration phenomenon, the prepared paste is printed with severe printing broken lines, the volume resistance is rapidly increased, the contact resistance is greatly increased, and the overall performance of HJT low-temperature silver paste is seriously affected.
3. According to the preparation method of the superfine silver powder for HJT low-temperature silver paste, the pH and the temperature do not need to be specially adjusted in the production process, the reaction can be completed at normal temperature, and the reaction energy consumption is reduced; in addition, compared with the traditional process, the embodiment has the advantages of relatively simple process, shorter reaction time, greatly improved production efficiency and saved production cost. The formulation and silver powder preparation process of the examples are obviously superior to those of the comparative examples by comparing the basic performances of the examples and the comparative examples.
The above examples of the present invention are only examples for clearly illustrating the present invention, and are not limiting of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (4)
1. The preparation method of the superfine silver powder for HJT low-temperature silver paste is characterized by comprising the following steps of: the method comprises the following steps:
1) Uniformly mixing silver nitrate and deionized water according to the mass ratio of 1 (5-20), stirring and dissolving in a reaction kettle A, controlling the temperature to be (30+/-1) DEG C, and maintaining the time for 5-10min; then adding alkali solution according to the mass ratio of silver nitrate to alkali solution of 1 (2-3), wherein the mass ratio of alkali to water in the alkali solution is 1: (3-5) generating silver oxide suspension, and then adding a mixed dispersing agent into the suspension, wherein the total addition amount of the mixed dispersing agent is 5-30% of the mass of the silver nitrate;
2) Adding deionized water, vitamin C and a mixed dispersing agent into a reaction kettle B, wherein the mass ratio of the added vitamin C to the silver nitrate is (1-1.5): 1, the total added amount of the mixed dispersing agent is 5-30% of the mass of the silver nitrate, the temperature is controlled at (30+/-1) DEG C, and the time is maintained for 5-10min;
the mixed dispersing agent in the step 1) and the step 2) is the mixture of a dispersing agent A and a dispersing agent B, wherein the mass ratio of the dispersing agent A to the dispersing agent B is (10-20) 1, the dispersing agent A is selected from phosphorus element or sulfonic polyether modified acrylic resin, and the dispersing agent B is selected from imidazole or imidazole derivatives;
3) Slowly adding the solution in the reaction kettle B into the reaction kettle A at a constant speed for 5-10min, continuously stirring for 10-15min after all the solution is added, adding an alcohol solution which is equivalent to 1-2 per mill of the silver nitrate in mass and is dissolved with oleic acid for silver powder coating treatment, and rapidly separating the silver powder from the solution after 5-5-10min, wherein the mass concentration of the alcohol solution which is dissolved with oleic acid is 15-25%;
4) Adding silver powder obtained by separation in the previous step into a ball milling tank, and adding zirconium balls with the diameter of 1mm into the ball milling tank, wherein the mass ratio of silver nitrate to the zirconium balls is 1:4; adding alcohol, wherein the mass ratio of the silver nitrate to the alcohol is 1 (0.5-0.8), and ball milling for 2-5 hours according to 80-100 revolutions per minute; and then separating silver powder, alcohol and zirconium balls by using a 100-mesh screen, continuously separating the silver powder from the alcohol by using a suction filtration mode, and freeze-drying to obtain the superfine silver powder with tap density more than 5, wherein the particle size distribution of the silver powder is 0.20-0.23, the particle size distribution of the silver powder is 0.30-0.40, the particle size of the silver powder is 0.60-0.63, and the particle size is very concentrated.
2. The method for preparing ultrafine silver powder for HJT low-temperature silver paste according to claim 1, wherein: the dispersant A in the step 1 and the step 2) is selected from phosphorus element modified acrylic resin or sulfonic polyether modified acrylic resin; the dispersant B is selected from imidazole or methylimidazole.
3. The method for preparing ultrafine silver powder for HJT low-temperature silver paste according to claim 1, wherein: the rapid separation in the step 3) is realized by pumping filtration of silver powder and deionized water, and the silver powder is washed by alcohol with the mass concentration of 10-30% for the last two times.
4. The superfine silver powder for HJT low-temperature silver paste is characterized in that: the method for preparing the superfine silver powder for HJT low-temperature silver paste, which is obtained by adopting the method for preparing the superfine silver powder for HJT low-temperature silver paste, is the superfine silver powder with tap density of more than 5, has the particle size distribution of D10 of 0.20-0.23, D50 of 0.30-0.40 and D90 of 0.60-0.63, and has very concentrated particle size.
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