CN115846678A - Preparation method of super-hydrophobic high-dispersibility silver powder - Google Patents
Preparation method of super-hydrophobic high-dispersibility silver powder Download PDFInfo
- Publication number
- CN115846678A CN115846678A CN202310167710.2A CN202310167710A CN115846678A CN 115846678 A CN115846678 A CN 115846678A CN 202310167710 A CN202310167710 A CN 202310167710A CN 115846678 A CN115846678 A CN 115846678A
- Authority
- CN
- China
- Prior art keywords
- solution
- silver powder
- silver
- preparation
- reducing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000012360 testing method Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000006722 reduction reaction Methods 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 72
- 239000003638 chemical reducing agent Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 39
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000003607 modifier Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 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 20
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- 239000011668 ascorbic acid Substances 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 5
- 229960003656 ricinoleic acid Drugs 0.000 claims description 5
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 5
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 4
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 4
- 235000020778 linoleic acid Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 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 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 123
- 239000002270 dispersing agent Substances 0.000 abstract description 27
- 239000002245 particle Substances 0.000 abstract description 12
- 229910052709 silver Inorganic materials 0.000 abstract description 9
- 239000004332 silver Substances 0.000 abstract description 9
- 238000011946 reduction process Methods 0.000 abstract description 4
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 20
- 230000008569 process Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 238000000635 electron micrograph Methods 0.000 description 6
- 102220042174 rs141655687 Human genes 0.000 description 6
- 102220035083 rs199475898 Human genes 0.000 description 6
- 102220076495 rs200649587 Human genes 0.000 description 6
- 102220043159 rs587780996 Human genes 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to a preparation method of super-hydrophobic high-dispersibility silver powder, relating to the technical field of silver powder preparation and comprising the following steps: step S1: solution preparation, step S2: preparing an oxidant precursor solution, and step S3: reduction reaction, step S4: washing and drying the silver powder, and S5: ball-milling and dispersing the silver powder, and S6: and (4) sieving and testing the silver powder. The preparation method adopts the principle that the dispersing agent is dissolved in an alkaline solution and precipitated in the reduction process, and the dispersing agent is added into the oxidant precursor solution in advance to coat the silver particles in situ to obtain the silver powder with good dispersibility and strong hydrophobicity.
Description
Technical Field
The invention relates to the technical field of silver powder preparation, and particularly relates to a preparation method of super-hydrophobic high-dispersity silver powder.
Background
Silver powder is an important noble metal powder material, and is widely used in the fields of solar paste, electronic paste, conductive paste, electronic components and the like due to excellent electrical conductivity and thermal conductivity. The requirements on the granularity uniformity and the dispersibility of the silver powder in the fields are high, the silver powder with poor dispersibility is easy to agglomerate, the formed agglomerate can cause the silver paste to block meshes in the printing process, and the silver paste made of the silver powder with good dispersibility can better pass through a silk screen and can print a more compact conductive coating.
At present, the silver powder is mostly prepared at home and abroad by adopting a liquid phase reduction method, and a dispersant and a modifier are mostly used for solving the problem of agglomeration in the silver powder preparation process, so that the dispersibility and the uniformity of the silver powder are improved. The type, adding time and adding amount of the dispersing agent directly influence the action effect of the dispersing agent. The adding time of the dispersing agent determines the main action stage of the dispersing agent in the nucleation, growth and aggregation among silver particles, if the dispersing agent is added into the reduction reaction process, the dispersing agent mainly acts in the growth and aggregation among silver particles, and the uniformity of the finally synthesized silver powder is poor, for example, chinese patents CN1700360A (2005-05-09) and CN1660529A (2005-08-31) disclose a silver powder and a preparation method thereof, formaldehyde is added into a silver ammonia solution to prepare the silver powder, the dispersing agent is added after the formaldehyde is added into the silver ammonia solution, the size of the silver powder is difficult to control in the reduction process, aggregation growth exists, and the final product needs to remove aggregation blocks with the particle size larger than 8 um; chinese patent CN110666184A (2020-01-10) discloses a preparation method of a spherical silver powder, silver ammonia is added into ascorbic acid to prepare silver powder, a dispersing agent is added into the ascorbic acid, the finally prepared silver powder is poor in consistency, wide in particle size distribution, large particles of about 1.5um and small particles of about 0.5um, and the silver powder preparation comprises a plurality of silver powder chemical modification processes, so that the process is complex and the cost is high. The more the dispersant is added, the better the dispersing effect is, but the large amount of the dispersant increases the production cost of the silver powder, so that the silver powder is difficult to clean; for example, patent CN108714700a (2018-06-07) discloses a preparation method of monodisperse high crystalline silver powder, which adds a dispersant in an oxidant solution and a reducing agent solution, and simultaneously adds a large amount of stearic acid as a flocculating agent after reduction is finished, thereby greatly increasing the production cost of the silver powder and being not beneficial to industrial production.
In addition, silver paste manufacturers have high requirements for the stability of the silver powder, the silver powder synthesized at present has certain water absorption, secondary agglomeration can be caused due to partial moisture absorption in the storage process, and the agglomerated silver powder is further compacted in the transportation process, so that the use performance of the silver powder at the slurry end is finally influenced.
Disclosure of Invention
The invention aims to solve the problems of high cost, complex process, poor uniformity and dispersibility and difficulty in controlling the size of silver powder in the prior art, and provides a preparation method of super-hydrophobic high-dispersibility silver powder.
The purpose of the invention is realized by the following technical scheme:
a preparation method of super-hydrophobic high-dispersibility silver powder comprises the following steps:
step S1, solution preparation: respectively preparing a silver nitrate solution A, a reducing agent solution C, a regulator solution D and a dispersant-modifier E;
s2, preparing an oxidant precursor solution: rapidly adding the regulator solution D into the silver nitrate solution A under stirring, stirring for 5-10min to obtain an oxidant precursor solution B, rapidly adding the dispersant-modifier E into the oxidant precursor solution B, and stirring for 5-30min;
step S3, reduction reaction: adding the reducing agent solution C into the reaction liquid synthesized in the step S2 through a flowmeter under stirring, and controlling the adding flow of the reducing agent solution C to be 1-10 equivalent; after the reducing agent solution C is added, reacting and aging;
step S4, centrifugal washing: transferring the silver powder obtained in the step S3 into a centrifuge, repeatedly washing the silver powder with deionized water until the conductivity is less than 20 mu S/cm, and collecting the silver powder for later use;
s5, drying and ball milling: drying the silver powder collected in the step S4 in a forced air drying oven at the temperature of 60-80 ℃, and performing ball milling and dispersion treatment on the dried silver powder;
step S6, sieving and testing: and (4) passing the ball-milled and dispersed silver powder through a 200-mesh screen to obtain a silver powder product, and testing.
Preferably, in the step S1, the preparation of the silver nitrate solution a: dissolving silver nitrate in deionized water to a mass concentration of 10-30% by weight, and controlling the solution temperature to 30-60 deg.C to obtain silver nitrate solution A.
Preferably, in step S1, preparation of the reducing agent solution C: dissolving a reducing agent in deionized water, wherein the mass of the reducing agent is 0.5-2 times of that of silver nitrate, the concentration of the reducing agent is 50-300g/L, the temperature of the solution is controlled to be 30-60 ℃, and a reducing agent solution C is prepared, wherein the reducing agent is one or more of ascorbic acid and formaldehyde.
Preferably, in the step S1, the preparation of the regulator solution D: dissolving a regulator in deionized water, wherein the mass of the regulator is 0.5-3 times of that of silver nitrate, the concentration of the regulator is 20-200g/L, and the temperature of the solution is controlled to be 30-60 ℃, wherein the regulator is one or more of sodium hydroxide, ammonia water and sodium carbonate.
Preferably, in step S1, the dispersant-modifier E is directly used in a solid or liquid form, and the mass of the dispersant & modifier is 0.2-1wt% of the mass of the reduced silver powder, wherein the dispersant & modifier is one or more of oleic acid, ricinoleic acid, linoleic acid, and stearic acid.
Preferably, in the step S2, the dispersant-modifier E is directly added to the silver oxide, silver ammonia, and silver carbonate precursor solution.
Preferably, in the step S3, the aging temperature for reacting and aging for a certain time is 30-60 ℃, and the aging time is 2-10min.
The technical scheme has the following beneficial effects:
1. according to the preparation method of the super-hydrophobic high-dispersibility silver powder, the dispersing agent is added into the silver oxide, silver carbonate and silver ammonia solution, so that the dispersing agent can play a dispersing role at the beginning of reduction, and the synthesized silver powder is controllable in shape and good in dispersibility and uniformity.
2. According to the preparation method of the super-hydrophobic high-dispersibility silver powder, provided by the invention, the principle that oleic acid, stearic acid, ricinoleic acid and linoleic acid are dissolved in an alkaline solution and are separated out in an acidic solution is utilized, so that the oleic acid is uniformly dispersed in the solution at the early stage of reduction, and a dispersing agent is separated out along with the reduction of the pH value of the solution in the reduction process, so that the in-situ protective dispersion effect is realized.
3. According to the preparation method of the super-hydrophobic high-dispersity silver powder, provided by the invention, oleic acid, ricinoleic acid, stearic acid and linoleic acid have strong hydrophobicity, so that the generated silver crystal grains can be wrapped to prevent the silver crystal grains from continuously growing in the reduction process, and the probability of mutual collision and agglomeration among the silver crystal grains is reduced by using the strong hydrophobicity and the steric hindrance effect of the dispersing agent, so that the dispersity and uniformity of the silver powder are improved, the surface of a printed battery piece is ensured to have good smoothness, and the tension and line resistance data on a single battery piece have good stability.
4. According to the preparation method of the super-hydrophobic high-dispersibility silver powder, provided by the invention, the subsequent silver powder surface modification process is omitted, the silver powder preparation process is reduced, the cost is saved, and the industrialization is easy to realize.
5. According to the preparation method of the super-hydrophobic high-dispersity silver powder, the prepared silver powder has high hydrophobicity, and the silver powder is hydrophobic and layered in the washing process, so that the washing efficiency can be improved, and the water consumption for washing can be saved.
6. According to the preparation method of the super-hydrophobic high-dispersibility silver powder, the finally prepared silver powder can be stored for a long time, secondary agglomeration cannot occur in the transportation process, and the application effect of the silver powder at the slurry end is guaranteed. The grain diameter D10 of the synthesized silver powder is 0.1-0.2um, the D50 is 0.4-1.1 um, the D90 is 1.4-2 um, and the D95 is 1.6-2.5 um; the specific surface area is 1.2-1.8 m 2 (ii)/g; tap densityIs 4.5-6.5-g/cm 3 (ii) a The burnout rate at 550 ℃ is 0.15-1%.
Drawings
FIG. 1 is an electron micrograph of a silver powder in example 1 of the present invention;
FIG. 2 is an electron micrograph of a silver powder in example 2 of the present invention;
FIG. 3 is an electron micrograph of a silver powder in example 3 of the present invention;
FIG. 4 is an electron micrograph of a silver powder in example 4 of the present invention;
FIG. 5 is an electron micrograph of a silver powder in comparative example 1 of the present invention;
FIG. 6 is an electron micrograph of a silver powder in comparative example 2 of the present invention.
Detailed description of the preferred embodiments
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In examples 1 to 4, comparative examples 1 and 2, D10 to D95 were measured by a laser diffraction particle size distribution tester, a specific surface area was measured by an N2 desorption apparatus (X1000 analyzer, kubo Beijing), a burn-out rate was obtained by measuring the mass difference percentage before and after 1 hour of heat preservation at 550 ℃ in a muffle furnace, a tap density was measured by a TD type powder tap density tester, and the pore structure of the material was characterized.
Example 1 a method for preparing a superhydrophobic high-dispersibility silver powder, comprising the steps of:
step S1: preparation of solutions
Preparation of silver nitrate solution A
Accurately weighing 1.11kg of silver nitrate, dissolving in 10L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain a silver nitrate solution A.
Preparation of reducing agent solution C
Accurately weighing 2.22kg of ascorbic acid, dissolving in 10L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain a reducing agent solution C.
Preparation of regulator solution D
3.33kg of sodium hydroxide is accurately weighed and dissolved in 16.65L of deionized water, the temperature of the solution is controlled at 30-32 ℃, and the solution is stirred for 30min to prepare the regulator solution D.
Preparation of dispersant-modifier solution E:
2.22g of oleic acid is accurately weighed to obtain a dispersant-modifier solution E for later use.
Step S2: preparation of oxidant precursor solution B
And (3) quickly adding the regulator solution D into the silver nitrate solution A at the stirring speed of 300rpm, stirring for 5min, then quickly adding 5g of oleic acid, controlling the solution temperature at 30-32 ℃, and stirring for 30min to obtain a precursor solution B.
And step S3: reduction reaction
Adding the reducing agent solution C into the precursor solution B at the speed of 1L/min under the stirring speed of 300rpm, controlling the process temperature at 30-32 ℃, and aging for 2min after the addition is finished;
and step S4: washing and drying silver powder
And D, transferring the silver powder aged in the step S3 into a centrifuge, washing the silver powder by using deionized water until the conductivity is less than 20us/cm, and transferring the silver powder into an air-blowing drying oven to dry for 12 hours at the temperature of 80 ℃.
Step S5: ball milling and dispersing of silver powder
After the silver powder is primarily crushed, the silver powder is added into a 3L stainless steel tank and treated for 4 hours by a tank mill at 350 rpm.
Step S6: sieving and testing silver powder
And (4) screening the treated silver powder by a 200-mesh screen to obtain a silver powder product and testing.
The test results in example 1 above were as follows, D10=0.17um, D50=0.76um, D90=1.51um, D95=1.92um, and the specific surface area was 1.45m 2 (g), tap density 5.6g/cm 3 And the burning loss at 550 ℃ is 0.46 percent, and as can be seen from figure 1, the synthesized silver powder has better dispersibility and uniformity.
Embodiment 2 a method for preparing super-hydrophobic silver powder with high dispersibility, comprising the following steps:
step S1: preparation of solutions
Preparation of silver nitrate solution A
Accurately weighing 1.5kg of silver nitrate, dissolving in 15L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain a silver nitrate solution A.
Preparation of reducing agent solution C
Accurately weighing 0.75kg of ascorbic acid, dissolving in 15L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain a reducing agent solution C.
Preparation of regulator solution D
Accurately weighing 0.75kg of sodium hydroxide, dissolving in 37.5L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain the regulator solution D.
Preparation of dispersant-modifier solution E:
accurately weighing 15g of oleic acid to obtain a dispersant-modifier solution E for later use.
Step S2: oxidant precursor preparation
And (3) quickly adding the regulator solution D into the silver nitrate solution A at the stirring speed of 300rpm, stirring for 5min, then quickly adding 2g of oleic acid, controlling the solution temperature at 30-32 ℃, and stirring for 30min to obtain a precursor solution B.
And step S3: reduction reaction
Adding the reducing agent solution C into the precursor solution B at the speed of 1L/min under the stirring speed of 300rpm, controlling the process temperature at 30-32 ℃, and aging for 2min after the addition is finished;
and step S4: washing and drying silver powder
And D, transferring the silver powder aged in the step S3 into a centrifuge, washing the silver powder by using deionized water until the conductivity is less than 20us/cm, and transferring the silver powder into an air-blowing drying oven to dry for 12 hours at the temperature of 80 ℃.
Step S5: ball milling and dispersing of silver powder
After the silver powder is primarily crushed, the silver powder is added into a 3L stainless steel tank and treated for 4 hours by a tank mill at 350 rpm.
Step S6: sieving and testing silver powder
And (4) screening the treated silver powder by a 200-mesh screen to obtain a silver powder product and testing.
The test results in example 2 above were as follows, D10=0.15um, D50=0.82um, D90=1.61um, D95=2.01um, specific surface area 1.35m 2 G, tap density 5.2g/cm 3 As can be seen from FIG. 2, when the amount of the dispersant used was small, the silver powder synthesized had less large particles.
Example 3 a super-hydrophobic high-dispersibility silver powder was prepared by the following steps:
step S1: preparation of solutions
Preparation of silver nitrate solution A
Accurately weighing 3.33kg of silver nitrate, dissolving in 10L of deionized water, controlling the temperature of the solution at 58-60 ℃, and stirring for 30min to obtain a silver nitrate solution A.
Preparation of reducing agent solution C
Accurately weighing 1.5kg of ascorbic acid and 1.5kg of formaldehyde, dissolving in 10L of deionized water, controlling the temperature of the solution at 58-60 ℃, and stirring for 30min to obtain a reducing agent solution C.
Preparation of regulator solution D
Accurately weighing 0.665kg of sodium hydroxide and 1kg of sodium carbonate, dissolving in 16.65L of deionized water, controlling the temperature of the solution at 58-60 ℃, and stirring for 30min to obtain a regulator solution D.
Preparation of dispersant-modifier solution E:
10g of stearic acid is accurately weighed to obtain a dispersant and modifier solid E for later use.
Step S2: oxidant precursor preparation
And (3) quickly adding the regulator solution D into the silver nitrate solution A at the stirring speed of 300rpm, stirring for 7min, then quickly adding 10g of oleic acid, controlling the solution temperature at 58-60 ℃, and stirring for 5min to obtain a precursor solution B.
And step S3: reduction reaction
Adding the reducing agent solution C into the precursor solution B at the speed of 1L/min under the stirring speed of 300rpm, controlling the process temperature at 30-32 ℃, and aging for 6min after the addition is finished;
and step S4: washing and drying silver powder
And D, transferring the silver powder aged in the step S3 into a centrifuge, washing the silver powder by using deionized water until the conductivity is less than 20us/cm, and transferring the silver powder into an air-blowing drying oven to dry for 12 hours at 70 ℃.
Step S5: ball milling and dispersing of silver powder
After the silver powder is primarily crushed, the silver powder is added into a 3L stainless steel can and processed for 4h by a can grinder at 350 rpm.
Step S6: sieving and testing silver powder
And (4) screening the treated silver powder by a 200-mesh screen to obtain a silver powder product and testing.
Test in example 3 aboveThe results were as follows, D10=0.12um, D50=0.43um, D90=1.43um, D95=1.72um, and the specific surface area was 1.61m 2 (g), tap density 6.1g/cm 3 And the burnout at 550 ℃ is 0.86%, and as can be seen from FIG. 3, the amount of the dispersant used is increased and the size of the silver powder is reduced.
Example 4a super-hydrophobic high-dispersibility silver powder was prepared by the following steps:
step S1: preparation of solutions
Preparation of silver nitrate solution A
Accurately weighing 1.5kg of silver nitrate, dissolving in 15L of deionized water, controlling the temperature of the solution at 44-46 ℃, and stirring for 30min to obtain a silver nitrate solution A.
Preparation of reducing agent solution C
Accurately weighing 1.5kg ascorbic acid to dissolve in 5L deionized water, accurately weighing 1.5kg 37% formaldehyde water solution, and mixing the two to obtain reducing agent C.
Preparation of regulator solution D
3.5kg of 28% ammonia water solution is accurately weighed, and the temperature is controlled to be 44-46 ℃ to prepare the regulator solution D.
Preparation of dispersant-modifier solution E:
5g of ricinoleic acid and linoleic acid are accurately weighed to obtain a dispersant and modifier liquid E for later use.
Step S2: oxidant precursor preparation
And (2) rapidly adding the regulator solution D into the silver nitrate solution A at the stirring speed of 300rpm, stirring for 10min, then rapidly adding 5g of stearic acid solid, controlling the solution temperature at 44-46 ℃, and stirring for 18min to obtain a precursor solution B.
And step S3: reduction reaction
Adding the reducing agent solution C into the precursor solution B at the speed of 1L/min under the stirring speed of 300rpm, controlling the process temperature at 44-46 ℃, and aging for 10min after the addition is finished;
and step S4: washing and drying silver powder
And D, transferring the silver powder aged in the step S3 into a centrifuge, washing the silver powder by using deionized water until the conductivity is less than 20us/cm, and transferring the silver powder into an air drying oven to dry for 12 hours at the temperature of 60 ℃.
Step S5: ball milling and dispersing of silver powder
After the silver powder is primarily crushed, the silver powder is added into a 3L stainless steel tank and treated for 4 hours by a tank mill at 350 rpm.
Step S6: sieving and testing silver powder
And (4) screening the treated silver powder by a 200-mesh screen to obtain a silver powder product and testing.
The test results in example 4 above were as follows, D10=0.15um, D50=0.76um, D90=1.51um, D95=2.25um, and the specific surface area was 1.32m 2 G, tap density 5.2g/cm 3 0.42% burn-out at 550 ℃, and as can be seen from fig. 4, the silver powder synthesized by using stearic acid as the dispersant has good dispersibility but still has a small amount of large particles.
Comparative example 1 this comparative example differs from example 1 in that:
step S1: preparation of solutions
Preparation of silver nitrate solution A
Accurately weighing 1.11kg of silver nitrate, dissolving in 10L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain a silver nitrate solution A.
Preparation of reducing agent solution C
Accurately weighing 3kg of ascorbic acid, dissolving in 8L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain a reducing agent solution C.
Preparation of regulator solution D
Accurately weighing 4kg of sodium hydroxide, dissolving in 20L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain a regulator solution D.
Preparation of dispersant-modifier solution E:
accurately weighing 20g of oleic acid to obtain a dispersant-modifier solution E for later use.
The test results in comparative example 1 described above were as follows, D10=0.1um, D50=0.19um, D90=1.34um, D95=1.51um, and specific surface area 1.82m 2 (g), tap density 5.6g/cm 3 The 550 ℃ burnout was 1.23%, as can be seen from FIG. 5, the reducing agent mass, the modifier mass, and the dispersant&When the mass of the modifier is larger, the reduction rate is higher, the synthesized silver powder particles are finer, and the size of the silver powder is difficult to control.
Comparative example 2 this comparative example differs from example 2 in that:
step S1: preparation of solutions
Preparation of silver nitrate solution A
Accurately weighing 1.5kg of silver nitrate, dissolving in 15L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain a silver nitrate solution A.
Preparation of reducing agent solution C
Accurately weighing 0.5 kg of ascorbic acid, dissolving in 15L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to obtain a reducing agent solution C.
Preparation of regulator solution D
Accurately weighing 0.5 kg of sodium hydroxide, dissolving in 30L of deionized water, controlling the temperature of the solution at 30-32 ℃, and stirring for 30min to prepare the regulator solution D.
Dispersant-modifier solution E preparation:
accurately weighing 2g of oleic acid to obtain a dispersant-modifier solution E for later use.
The test results in the above comparative example 2 were as follows, D10=0.25um, D50=1.36um, D90=2.67um, D95=3.342um, and the specific surface area was 0.82m 2 (g), tap density 4.65g/cm 3 0.38% of 550 ℃ burning loss, as can be seen from FIG. 6, when the reducing agent and the regulator are small in mass, the reduction rate is slow, the synthesis time is long, the silver powder particles further grow up, and meanwhile, the dispersing agent&When the modifier is low in quality, the silver powder is poor in consistency.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (7)
1. The preparation method of the super-hydrophobic high-dispersibility silver powder is characterized by comprising the following steps of:
step S1, solution preparation: respectively preparing a silver nitrate solution A, a reducing agent solution C, a regulator solution D and a dispersant-modifier E;
step S2, preparing an oxidant precursor solution: rapidly adding the regulator solution D into the silver nitrate solution A under stirring, stirring for 5-10min to obtain an oxidant precursor solution B, rapidly adding the dispersant-modifier E into the oxidant precursor solution B, and stirring for 5-30min;
step S3, reduction reaction: adding the reducing agent solution C into the reaction liquid synthesized in the step S2 through a flowmeter under stirring, and controlling the adding flow of the reducing agent solution C to be 1-10 equivalent; after the reducing agent solution C is added, reacting and aging;
step S4, centrifugal washing: transferring the silver powder obtained in the step S3 into a centrifuge, repeatedly washing the silver powder with deionized water until the conductivity is less than 20 mu S/cm, and collecting the silver powder for later use;
s5, drying and ball milling: drying the silver powder collected in the step S4 in a forced air drying oven at the temperature of 60-80 ℃, and performing ball milling and dispersion treatment on the dried silver powder;
step S6, sieving and testing: and (4) passing the ball-milled and dispersed silver powder through a 200-mesh screen to obtain a silver powder product, and testing.
2. The method for preparing the superhydrophobic high-dispersibility silver powder according to claim 1, wherein: in the step S1, preparing a silver nitrate solution A: dissolving silver nitrate in deionized water to a mass concentration of 10-30% by weight, and controlling the solution temperature to 30-60 deg.C to obtain silver nitrate solution A.
3. The method for preparing the superhydrophobic high-dispersibility silver powder according to claim 2, wherein: in the step S1, preparation of a reducing agent solution C: dissolving a reducing agent in deionized water, wherein the mass of the reducing agent is 0.5-2 times of that of silver nitrate, the concentration of the reducing agent is 50-300g/L, the temperature of the solution is controlled to be 30-60 ℃, and a reducing agent solution C is prepared, wherein the reducing agent is one or more of ascorbic acid and formaldehyde.
4. The method for preparing the superhydrophobic high-dispersibility silver powder according to claim 3, wherein: in the step S1, preparation of a regulator solution D: dissolving a regulator in deionized water, wherein the quality of the regulator is 0.5-3 times of that of silver nitrate, the concentration of the regulator is 20-200g/L, and the temperature of the solution is controlled to be 30-60 ℃, wherein the regulator is one or more of sodium hydroxide, ammonia water and sodium carbonate.
5. The method for preparing the superhydrophobic high-dispersibility silver powder according to claim 4, wherein: in the step S1, the dispersant-modifier E is directly used in a solid or liquid form, the mass of the dispersant-modifier E is 0.2-1wt% of the mass of the reduced silver powder, wherein the dispersant-modifier E is one or more of oleic acid, ricinoleic acid, linoleic acid and stearic acid.
6. The method for preparing the superhydrophobic high-dispersibility silver powder according to claim 5, wherein: in the step S2, the dispersant-modifier E is directly added into the precursor solution of silver oxide, silver ammonia and silver carbonate.
7. The method for preparing the superhydrophobic high-dispersibility silver powder according to claim 6, wherein: in the step S3, the aging temperature for reacting and aging for a certain time is 30-60 ℃, and the aging time is 2-10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310167710.2A CN115846678A (en) | 2023-02-27 | 2023-02-27 | Preparation method of super-hydrophobic high-dispersibility silver powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310167710.2A CN115846678A (en) | 2023-02-27 | 2023-02-27 | Preparation method of super-hydrophobic high-dispersibility silver powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115846678A true CN115846678A (en) | 2023-03-28 |
Family
ID=85659052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310167710.2A Pending CN115846678A (en) | 2023-02-27 | 2023-02-27 | Preparation method of super-hydrophobic high-dispersibility silver powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115846678A (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660529A (en) * | 2004-02-26 | 2005-08-31 | 同和矿业株式会社 | Silver powder and its mfg.process |
| CN1700360A (en) * | 2004-05-19 | 2005-11-23 | 同和矿业株式会社 | Spherical silver powder and method for producing same |
| JP2015054975A (en) * | 2013-09-10 | 2015-03-23 | 住友金属鉱山株式会社 | Silver powder and method for producing the same |
| CN106862588A (en) * | 2017-01-23 | 2017-06-20 | 湖南省国银新材料有限公司 | A kind of preparation method of laser engraving touch-screen silver paste super fine silver powder |
| CN107538015A (en) * | 2016-06-23 | 2018-01-05 | 扬中市润宇电力设备有限公司 | Solar cell front side silver paste silver powder and preparation method thereof |
| CN107661986A (en) * | 2017-08-03 | 2018-02-06 | 昆明贵金属研究所 | A kind of method for being prepared on a large scale the high sphericity super fine silver powder of high dispersive |
| CN108714700A (en) * | 2018-06-07 | 2018-10-30 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method of the highly crystalline type silver powder of monodisperse and its silver powder obtained |
| CN110586959A (en) * | 2019-10-28 | 2019-12-20 | 苏州银瑞光电材料科技有限公司 | Preparation method of flake silver powder with high tap density |
| CN110666184A (en) * | 2019-10-28 | 2020-01-10 | 苏州银瑞光电材料科技有限公司 | Preparation method of sphere-like silver powder |
| CN111889698A (en) * | 2020-09-01 | 2020-11-06 | 苏州银瑞光电材料科技有限公司 | Preparation method of superfine spherical silver powder |
| CN113399678A (en) * | 2021-05-08 | 2021-09-17 | 东方电气集团科学技术研究院有限公司 | Preparation method of low-cost high-dispersion superfine silver powder |
| CN113618077A (en) * | 2021-08-05 | 2021-11-09 | 江苏正能电子科技有限公司 | Modified silver powder for improving PERC back silver conversion efficiency and preparation method thereof |
| CN114367674A (en) * | 2022-03-22 | 2022-04-19 | 南通领跑者新材料科技有限公司 | Method for preparing silver powder |
| CN114472917A (en) * | 2022-02-11 | 2022-05-13 | 西安汇创贵金属新材料研究院有限公司 | Preparation method of high-dispersity submicron silver powder |
-
2023
- 2023-02-27 CN CN202310167710.2A patent/CN115846678A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660529A (en) * | 2004-02-26 | 2005-08-31 | 同和矿业株式会社 | Silver powder and its mfg.process |
| CN1700360A (en) * | 2004-05-19 | 2005-11-23 | 同和矿业株式会社 | Spherical silver powder and method for producing same |
| JP2015054975A (en) * | 2013-09-10 | 2015-03-23 | 住友金属鉱山株式会社 | Silver powder and method for producing the same |
| CN107538015A (en) * | 2016-06-23 | 2018-01-05 | 扬中市润宇电力设备有限公司 | Solar cell front side silver paste silver powder and preparation method thereof |
| CN106862588A (en) * | 2017-01-23 | 2017-06-20 | 湖南省国银新材料有限公司 | A kind of preparation method of laser engraving touch-screen silver paste super fine silver powder |
| CN107661986A (en) * | 2017-08-03 | 2018-02-06 | 昆明贵金属研究所 | A kind of method for being prepared on a large scale the high sphericity super fine silver powder of high dispersive |
| CN108714700A (en) * | 2018-06-07 | 2018-10-30 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method of the highly crystalline type silver powder of monodisperse and its silver powder obtained |
| CN110586959A (en) * | 2019-10-28 | 2019-12-20 | 苏州银瑞光电材料科技有限公司 | Preparation method of flake silver powder with high tap density |
| CN110666184A (en) * | 2019-10-28 | 2020-01-10 | 苏州银瑞光电材料科技有限公司 | Preparation method of sphere-like silver powder |
| CN111889698A (en) * | 2020-09-01 | 2020-11-06 | 苏州银瑞光电材料科技有限公司 | Preparation method of superfine spherical silver powder |
| CN113399678A (en) * | 2021-05-08 | 2021-09-17 | 东方电气集团科学技术研究院有限公司 | Preparation method of low-cost high-dispersion superfine silver powder |
| CN113618077A (en) * | 2021-08-05 | 2021-11-09 | 江苏正能电子科技有限公司 | Modified silver powder for improving PERC back silver conversion efficiency and preparation method thereof |
| CN114472917A (en) * | 2022-02-11 | 2022-05-13 | 西安汇创贵金属新材料研究院有限公司 | Preparation method of high-dispersity submicron silver powder |
| CN114367674A (en) * | 2022-03-22 | 2022-04-19 | 南通领跑者新材料科技有限公司 | Method for preparing silver powder |
Non-Patent Citations (2)
| Title |
|---|
| 刘瑜: "丙三醇还原制备银粉中碱用量对银粉粒度的影响" * |
| 秦智: "高分散性球形银粉的制备研究" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110434355B (en) | Preparation method of high-tap-density and high-dispersibility spherical silver powder | |
| CN109128141B (en) | Preparation method of nano WC-Co composite powder | |
| CN110611098B (en) | High-radiation and high-tap-density nickel-cobalt lithium aluminate precursor and preparation method thereof | |
| CN101066781B (en) | Process of preparing cobalto-cobaltic oxide for lithium ion cell | |
| WO2013021974A1 (en) | Nickel oxide micropowder and method for producing same | |
| CN113399679A (en) | Preparation method of high-tap aging-resistant superfine silver powder for electronic paste | |
| CN114133240B (en) | Method for preparing scandium-cerium-ytterbium-doped zirconia superfine powder by hydrolysis-hydrothermal method | |
| CN117380966B (en) | Preparation method of polycrystalline structure silver powder with controllable grain size | |
| CN115465904A (en) | Process for preparing nano iridium dioxide through strong dispersion | |
| CN116967461A (en) | High-dispersion low-burning-loss superfine silver powder and preparation method thereof | |
| CN115846678A (en) | Preparation method of super-hydrophobic high-dispersibility silver powder | |
| CN113292097A (en) | Method for preparing high-tetragonality barium titanate powder | |
| CN112264629A (en) | Preparation method and application of low-cost high-dispersion silver powder | |
| CN116329567A (en) | Method for preparing high-dispersion microcrystalline silver powder by two-step method and microchannel reaction equipment | |
| CN114436314A (en) | Preparation method of nano yttrium oxide, nano yttrium oxide and yttrium oxide micron hollow sphere | |
| CN114105228B (en) | Preparation method of ruthenium oxide for thick film resistor | |
| CN115863570A (en) | Preparation method of sodium ferric sulfate cathode material | |
| CN115196970A (en) | Preparation method of high-fluidity AlON spherical powder | |
| CN107777718A (en) | A kind of Y2O3Nano-powder and preparation method thereof | |
| CN113084189A (en) | Preparation method of silver powder | |
| CN111533149A (en) | Preparation method of light high-dispersion calcium oxide | |
| CN111014717A (en) | Silver powder for low-temperature curing conductive silver paste and preparation method thereof | |
| CN102581289B (en) | Method for preparing monodisperse high-crystallinity silver powder | |
| CN105817646B (en) | A kind of preparation method of the ball shape silver powder of high-tap density | |
| CN110434352A (en) | A kind of low-temperature cured conductive silver paste silver powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230328 |